CN110776387A - Device for preparing salt-free compound amino acid by using cystine production waste liquid - Google Patents
Device for preparing salt-free compound amino acid by using cystine production waste liquid Download PDFInfo
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Abstract
The invention belongs to the technical field of salt-free compound amino acid preparation, and discloses a device for preparing salt-free compound amino acid by using cystine production waste liquid, which comprises a bipolar membrane electrodialysis system, a mixing chamber and a homogeneous membrane electrodialysis system, wherein the bipolar membrane electrodialysis system and the homogeneous membrane electrodialysis system respectively comprise electrode chambers on two sides and one or more chamber units clamped between the two electrode chambers, and cystine mother liquid is divided into two parts, wherein one part is acidic mother liquid with the pH value of 2.5-3, the other part is alkaline mother liquid with the pH value of 10.5-11, and the salt is removed by the bipolar membrane electrodialysis system, so that the amino acid cannot be lost into an acid solution or an alkali solution, the aim of complete extraction is fulfilled, and the aim of recovering acid and alkali can be fulfilled; on one hand, the homogeneous membrane electrodialysis system can further desalt, and on the other hand, the brine is merged into the original mother liquor for recycling, so that the problem of wastewater treatment can be solved.
Description
Technical Field
The invention relates to the technical field of salt-free compound amino acid preparation, in particular to a device for preparing salt-free compound amino acid by using cystine production waste liquid.
Background
The production of cystine (L-cysteine, cyss) generally adopts a scleroprotein hydrolysis method, firstly uses hydrochloric acid to carry out acid hydrolysis on animal hair, then uses alkali (sodium oxide or ammonia water) to neutralize the hydrolysate to prepare the L-cystine (L-cysteine, cyss), and the mother liquor after extracting cystine contains 17 amino acids, so that the L-cystine (L-cystine, cyss) is very suitable to be used as a raw material of feed and fertilizer, and is also a national encouragement project. However, in the process for producing cystine by keratin hydrolysis method, a large amount of salt (sodium chloride or ammonium chloride) is necessarily generated by acid-base neutralization, and the amino acid content of the obtained product is about 40% and the sodium (ammonium) chloride content is about 40% after the mother liquor is directly dried into powder. And the salt-containing compound amino acid and the salt-free compound amino acid have the following defects:
(1) the market price of the salt-containing compound amino acid is about 2000 yuan/ton, the drying cost is about 1000 yuan, a large amount of resources and energy are consumed, the economic value is low, and the resource waste is caused;
(2) the non-salt compound amino acid can replace EDTA to be used as a metal trace element (copper, iron, zinc, manganese, magnesium, calcium and the like) chelate carrier, so that inorganic metal trace elements are chelated into organic metal elements to be better absorbed by animals and plants, but the chelating rate of the salt-containing compound amino acid is extremely low, and when the non-salt compound amino acid is used for feeds and fertilizers, the absorption rate is low, the effect is poor, heavy metal harm to agricultural products can be caused, unsafe factors are brought to the foods, and the environmental pollution can be caused;
(3) the salt-free compound amino acid is an efficient plant nutrient, can enhance the ice resistance and insect resistance of plants, greatly reduces the pesticide consumption, is beneficial to improving the edible safety of agricultural products, can culture microorganisms in soil, and achieves the aim of improving the soil through the metabolism of the microorganisms;
in combination with the above reasons, people pay more and more attention to food safety, and the national regulations on the fertilizer market are more and more strict, so that the demand of the market on the salt-free compound amino acid is more and more increased, and some enterprises try to develop a method which is feasible for scale and low in cost to prepare the salt-free compound amino acid by desalting, but none of the methods is successfully used for scale production. The current methods generally used to prepare salt-free complex amino acids are mainly three:
the first is ion exchange resin method, i.e. anion exchange resin is used to adsorb chloride ions in sodium (ammonium) chloride in mother liquor, and cation exchange resin is used to adsorb sodium (ammonium) ions, so as to achieve the aim of desalination. The method has the defects that the salt content in the mother liquor is as high as 15-20%, so that a large amount of dilution is needed, and a large amount of concentration is needed after the later desalting, so that the cost is high, in addition, a large amount of acid-base solution is needed for regenerating the resin, and a large amount of waste water is generated to be treated.
Secondly, animal hair is hydrolyzed by sulfuric acid, and salt-free compound amino acid is prepared by a lime neutralization method, namely the production method currently used by the company, but the defects of the method are obviously sensed in the production process: a large amount of calcium sulfate waste residues are generated and can be used as fillers of organic compound fertilizers before, but the solid compound fertilizers are gradually replaced by water-soluble compound fertilizers at present, and the solid waste treatment also gradually falls into an embarrassing situation.
Thirdly, desalting is carried out by electrodialysis, which is mentioned in many documents, but only for a solution containing a single amino acid, because: various amino acids have different isoelectric points due to differences in their compositions and structures. The charged particles move under the influence of an electric field towards an electrode of opposite electrical polarity, known as Electrophoresis (EP). When the pH value of the amino acid solution is the same as the isoelectric point of an amino acid, the amino acid just exists in a dipolar ion form, namely, the number of positive charges and negative charges of the amino acid are equal, and the net charge is zero, namely, the amino acid is electrically neutral. In the electric field, the pH value is the isoelectric point (pI) of the amino acid, and the amino acid does not move to the negative electrode or the positive electrode. But the L-cystine mother liquor contains 17 free amino acids, 17 amino acids correspond to 17 different isoelectric points, wherein the isoelectric point of the neutral amino acid is less than 7, and is generally 5.0-6.5; the isoelectric point of the acidic amino acid is about 3; the isoelectric point of the basic amino acid is 7.58-10.8. When the pH value of the amino acid solution is more than pI, NH3 in the amino acid gives a proton, the equilibrium shifts to the right, then the amino acid mainly exists in an anion form, and the part of the amino acid with the pI less than the pH value of the solution moves to the positive pole through an anion membrane in an electric field; on the contrary, when the pH of the amino acid solution is less than pI, COO in the amino acid binds to protons to shift the equilibrium to the left, where the amino acid exists mainly in a cationic form, and moves to the negative electrode if the amino acid is in an electric field. Therefore, when the homogeneous membrane electrodialysis desalination is adopted, most of amino acids mainly pass through the anion-cation exchange membrane and the cation-anion exchange membrane respectively along with anions and cations to migrate into the brine in the concentrated water chamber; when adopting bipolar membrane electrodialysis, amino acid respectively passes through anion and cation membranes along with anions and cations and migrates to an acid-base collection chamber, and the purpose of collecting and extracting salt-free amino acid cannot be achieved.
In conclusion, many factors need to be considered in the production of the salt-free compound amino acid, and in addition, although the salt-free compound amino acid has great significance in the fields of food safety, soil protection and the like, the salt-free compound amino acid can be used in the market after being clean, environment-friendly and appropriate in cost in the production process, so that the salt-free compound amino acid can be popularized in a large range and brings economic benefits.
Disclosure of Invention
The invention aims to: the utility model provides an utilize cystine production waste liquid preparation no salt compound amino acid's device problem of extracting preparation 17 no salt amino acids that can utilize production cystine mother liquor reasonable, high-efficient, environmental protection to lack among the prior art.
The technical scheme adopted by the invention is as follows:
the device comprises a bipolar membrane electrodialysis system, a mixing chamber and a homogeneous membrane electrodialysis system, wherein the bipolar membrane electrodialysis system and the homogeneous membrane electrodialysis system respectively comprise electrode chambers on two sides and one or more chamber units clamped between the two electrode chambers, each chamber in the bipolar membrane electrodialysis system and the homogeneous membrane electrodialysis system respectively forms a corresponding circulation loop with a circulating pump and a collecting box, and the mixing chamber is used for adjusting the pH value of a mixed solution of an acidic mother solution and an alkaline mother solution.
Further, in the bipolar membrane electrodialysis system, each chamber unit is composed of an acid circulation chamber I, an acid mother liquor circulation chamber II, an alkaline mother liquor circulation chamber I, an alkaline circulation chamber I, an acid circulation chamber II, an acid mother liquor circulation chamber III, an alkaline mother liquor circulation chamber II, an alkaline mother liquor circulation chamber III and an alkaline circulation chamber II which are sequentially arranged; the electrode chamber adjacent to the first acid circulation chamber is an anode chamber, the anode chamber and the first acid circulation chamber are separated by a bipolar membrane, the electrode chamber adjacent to the second alkali circulation chamber is a cathode chamber, and the cathode chamber and the second alkali circulation chamber are separated by the bipolar membrane; anion exchange membranes are respectively used as intervals between the first acid circulation chamber and the first acid mother liquor circulation chamber, between the first acid mother liquor circulation chamber and the second acid mother liquor circulation chamber, between the second acid circulation chamber and the third acid mother liquor circulation chamber, and between the third acid mother liquor circulation chamber and the second alkaline mother liquor circulation chamber, and cation exchange membranes are respectively used as intervals between the second acid mother liquor circulation chamber and the first alkaline mother liquor circulation chamber, between the first alkaline mother liquor circulation chamber and the first alkaline circulation chamber, between the second alkaline mother liquor circulation chamber and the third alkaline mother liquor circulation chamber, and between the third alkaline mother liquor circulation chamber and the second alkaline circulation chamber; the pH range of the acidic mother liquor is 2.5-3, and the pH range of the alkaline mother liquor is 10.5-11; if a plurality of cavity units exist, adjacent cavity units are separated by the bipolar membrane.
Furthermore, in the homogeneous membrane electrodialysis system, each chamber unit consists of a concentrated water chamber I, a fresh water chamber I, a concentrated water chamber II, a fresh water chamber II and a concentrated water chamber III which are sequentially arranged; the electrode chamber adjacent to the first concentrated water chamber is an anode chamber, the anode chamber and the first concentrated water chamber are separated by a bipolar membrane, the electrode chamber adjacent to the third concentrated water chamber is a cathode chamber, and the cathode chamber and the third concentrated water chamber are separated by the bipolar membrane; cation exchange membranes are respectively used as intervals between the first concentrated water chamber and the first fresh water chamber, and between the second concentrated water chamber and the second fresh water chamber, and anion exchange membranes are respectively used as intervals between the first fresh water chamber and the second concentrated water chamber, and between the second fresh water chamber and the third concentrated water chamber; if a plurality of cavity units are provided, adjacent cavity units are arranged in sequence by taking the bipolar membrane as an interval or directly.
Furthermore, the mixing chamber is provided with an acidic mother liquor inlet and an alkaline mother liquor inlet, the acidic mother liquor inlet is connected with an acidic mother liquor collecting box in the bipolar membrane electrodialysis system through a pipeline, the alkaline mother liquor inlet is connected with an alkaline mother liquor collecting box in the bipolar membrane electrodialysis system through a pipeline, and the two pipelines are respectively provided with a control valve.
Furthermore, the mixing chamber is also provided with a mixed liquid outlet, the mixed liquid outlet is connected with a mother liquid collecting box in the homogeneous membrane electrodialysis system through a pipeline, and the pipeline is provided with a control valve.
Further, in the bipolar membrane electrodialysis system and the homogeneous membrane electrodialysis system, 0.2% of Na is respectively added into the two electrode chambers
2SO
4Solutions of
Further, a flow meter is also included in the circulation loop.
Furthermore, in the homogeneous membrane electrodialysis system, aqueous solutions are respectively added into the first concentrated water chamber, the second concentrated water chamber and the third concentrated water chamber.
The working principle of the invention is as follows: the cystine mother liquor contains 17 amino acids, and the isoelectric points of the amino acids are different, wherein the lowest isoelectric point is aspartic acid pI being 3, and the highest isoelectric point is arginine pI being 10.8, so that the cystine mother liquor is divided into two parts, one part is adjusted to pH 2.5-3 to be used as acidic mother liquor and injected into an acidic mother liquor collecting box, and the other part is adjusted to pH 10.5-11 to be used as alkaline mother liquor and injected into an alkaline mother liquor collecting box.
The acid mother liquor is absorbed into a first acid mother liquor circulating chamber, a second acid mother liquor circulating chamber and a third acid mother liquor circulating chamber by direct current in a bipolar membrane electrodialysis system and starting a circulating pump of each chamber, the acid mother liquor is absorbed into the first acid mother liquor circulating chamber, the second acid mother liquor circulating chamber and the third acid mother liquor circulating chamber, the pH value of the acid mother liquor is smaller than the isoelectric point of all amino acids in the mother liquor, so that all the amino acids are positively charged and cannot migrate to a first acid circulating chamber or the second acid circulating chamber through an anion exchange membrane, anions in the first acid mother liquor circulating chamber, the second acid mother liquor circulating chamber and the third acid mother liquor circulating chamber penetrate through the anion exchange membrane and are combined with hydrogen ions generated on the bipolar membrane to form an acid solution in the first acid circulating chamber or the second acid circulating chamber, the amino acids with positive charges in the second acid mother liquor circulating chamber migrate to a first alkaline mother liquor circulating chamber through the cation exchange membrane, and the cations, the positive ions and hydroxide ions generated on the bipolar membrane react to produce an alkali solution, and amino acid is converted from positive charges into negative charges after entering the first alkaline mother liquor circulating chamber, cannot migrate into the first alkaline circulating chamber through the cation exchange membrane, and is completely trapped in the first alkaline mother liquor circulating chamber.
The alkaline mother liquor is sucked into the first acidic mother liquor circulating chamber, the second alkaline mother liquor circulating chamber and the third alkaline mother liquor circulating chamber, because the pH value of the alkaline mother liquor is greater than the isoelectric point of all amino acids in the mother liquor, all the amino acids are negatively charged and cannot migrate to the first alkali circulation chamber or the second alkali circulation chamber through the cation exchange membrane, cations in the first alkaline mother liquor circulating chamber, the second alkaline mother liquor circulating chamber and the third alkaline mother liquor circulating chamber are combined in the first alkaline circulating chamber or the second alkaline circulating chamber through the cation exchange membrane and hydroxide ions generated on the bipolar membrane to form an alkaline solution, amino acid with negative charges in the second alkaline mother liquor circulating chamber is transferred to the third acidic mother liquor circulating chamber along with anions in the mother liquor through the anion exchange membrane, the anions continue to permeate the anion exchange membrane and migrate into the acid circulation chamber II, and the anions react with hydrogen ions generated on the bipolar membrane to produce an acid solution; and after the amino acid enters the third acid mother liquor circulating chamber, the negative charges are converted into positive charges, the positive charges cannot migrate into the first acid circulating chamber through an anion exchange membrane, and the amino acids are all trapped in the third acid mother liquor circulating chamber.
Each chamber, the circulating pump connected with the chamber and the collecting box form a circulating loop respectively, wherein the acidic mother liquor circulating chamber I, the acidic mother liquor circulating chamber II and the acidic mother liquor circulating chamber III of all the chamber units can share one circulating pump and one acidic mother liquor collecting box; the first alkaline mother liquor circulating chamber, the second alkaline mother liquor circulating chamber and the third alkaline mother liquor circulating chamber of all the cavity units can share one circulating pump and one alkaline mother liquor collecting box; the acid circulation chambers I and II of all the cavity units can share one circulation pump and one acid liquid collection box; the first alkali circulation chamber and the second alkali circulation chamber of all the cavity unit can share one circulating pump and one alkali liquor collecting box;
when the anions in the acid mother liquor collecting box and the cations in the alkaline solution collecting box are detected to reach the required targets, adding the two parts of mother liquor into a mixing chamber for neutralization, adjusting the mixed mother liquor to be neutral, wherein the pH value of the compound amino acid is about 5-6, and a small amount of new salt can be formed by the neutralization of the acid-base solution during mixing;
then, the mother liquor in the mixing chamber after neutralization is added into a homogeneous membrane electrodialysis system for desalination treatment, a direct current is passed through the homogeneous membrane electrodialysis system, a circulating pump of each chamber is started, the mother liquor is sucked into a fresh water chamber, cations in the mother liquor permeate a cation exchange membrane, anions permeate an anion exchange membrane, and anions and cations are combined in a concentrated water chamber to form salt, wherein a small amount of amino acid enters the concentrated water chamber, but the solution in the concentrated water chamber is finally and completely returned to the original mother liquor for recycling, so that the amino acid is not lost, and the problem of wastewater treatment is solved;
each chamber and the circulating pump and the collecting box connected with each chamber form a circulating loop respectively, wherein the concentrated water chambers of all the chamber units can share one circulating pump and one brine collecting box; the fresh water chambers of all the cavity units can share one circulating pump and one mother liquor collecting box;
after the desalting treatment of the homogeneous membrane electrodialysis system is finished, the salt-free compound amino acid solution is obtained in a mother liquor collection box, and the salt-free compound amino acid product can be obtained through conventional subsequent treatment (spray drying).
In summary, due to the adoption of the technical scheme, the invention has the beneficial effects that:
1. the cystine mother liquor is divided into two parts, wherein one part is acidic mother liquor with the pH value of 2.5-3, the other part is alkaline mother liquor with the pH value of 10.5-11, and the alkaline mother liquor is desalted by a bipolar membrane electrodialysis system, so that amino acid cannot be lost into an acid solution or an alkaline solution, the aim of complete extraction is fulfilled, and the aim of recycling acid and alkali can be fulfilled; on one hand, the homogeneous membrane electrodialysis system can further desalt, and on the other hand, the problem of wastewater treatment can be solved by importing brine into the original mother liquor for recycling;
2. the salt content of the cystine mother liquor is usually 15% -18%, and the device provided by the invention can perform a desalting function on the amino acid solution with the salt content of 2% -20%;
3. the device provided by the invention has no potential safety hazard and no noise in the using process, is easy for automatic production, can normally run at normal temperature and normal pressure, is simple to implement and operate, can increase or decrease the unit number of chambers of the bipolar membrane electrodialysis system and the homogeneous membrane electrodialysis system according to the yield or the desalination amount, correspondingly increases or decreases the number of membranes, and can change the yield or the desalination amount by changing the effective area of the membranes;
4. the concentration of the recovered alkali solution can reach 4-6mol/L, the use concentration in the production of cystine is met, the alkali solution with high concentration can be prepared by concentration, the concentration of the recovered acid solution can reach 4-6mol/L, the method can be completely used for producing cystine, the production cost is reduced, and an environment-friendly production mode is realized;
5. the device provided by the invention is beneficial to realizing the safe and environment-friendly production of the salt-free compound amino acid, solves the bottleneck of large-scale and intelligent development, and is worthy of popularization and application.
Drawings
FIG. 1 is a schematic structural view of the present invention;
labeled as: 1-bipolar membrane electrodialysis system, 2-mixing chamber, 3-homogeneous membrane electrodialysis system.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely with reference to fig. 1 in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A device for preparing salt-free compound amino acid by using cystine production waste liquid comprises a bipolar membrane electrodialysis system 1, a mixing chamber 2 and a homogeneous membrane electrodialysis system 3, wherein the bipolar membrane electrodialysis system 1 and the homogeneous membrane electrodialysis system 3 respectively comprise electrode chambers on two sides and one or more chamber units clamped between the two electrode chambers, each of the bipolar membrane electrodialysis system 1 and the homogeneous membrane electrodialysis system 3 respectively forms a corresponding circulation loop with a circulating pump and a collecting box, and the mixing chamber 2 is used for adjusting the pH value of a mixed liquid of acidic mother liquid and alkaline mother liquid.
In the bipolar membrane electrodialysis system 1, each cavity unit is composed of an acid circulation chamber I, an acid mother liquor circulation chamber II, an alkaline mother liquor circulation chamber I, an alkaline circulation chamber I, an acid circulation chamber II, an acid mother liquor circulation chamber III, an alkaline mother liquor circulation chamber II, an alkaline mother liquor circulation chamber III and an alkaline circulation chamber II which are sequentially arranged; the electrode chamber adjacent to the first acid circulation chamber is an anode chamber, the anode chamber and the first acid circulation chamber are separated by a bipolar membrane, the electrode chamber adjacent to the second alkali circulation chamber is a cathode chamber, and the cathode chamber and the second alkali circulation chamber are separated by the bipolar membrane; anion exchange membranes are respectively used as intervals between the first acid circulation chamber and the first acid mother liquor circulation chamber, between the first acid mother liquor circulation chamber and the second acid mother liquor circulation chamber, between the second acid circulation chamber and the third acid mother liquor circulation chamber, and between the third acid mother liquor circulation chamber and the second alkaline mother liquor circulation chamber, and cation exchange membranes are respectively used as intervals between the second acid mother liquor circulation chamber and the first alkaline mother liquor circulation chamber, between the first alkaline mother liquor circulation chamber and the first alkaline circulation chamber, between the second alkaline mother liquor circulation chamber and the third alkaline mother liquor circulation chamber, and between the third alkaline mother liquor circulation chamber and the second alkaline circulation chamber; the pH range of the acidic mother liquor is 2.5-3, and the pH range of the alkaline mother liquor is 10.5-11; if a plurality of cavity units are provided, adjacent cavity units are separated by the bipolar membrane;
in the homogeneous membrane electrodialysis system, each chamber unit consists of a concentrated water chamber I, a fresh water chamber I, a concentrated water chamber II, a fresh water chamber II and a concentrated water chamber III which are sequentially arranged; the electrode chamber adjacent to the first concentrated water chamber is an anode chamber, the anode chamber and the first concentrated water chamber are separated by a bipolar membrane, the electrode chamber adjacent to the third concentrated water chamber is a cathode chamber, and the cathode chamber and the third concentrated water chamber are separated by the bipolar membrane; cation exchange membranes are respectively used as intervals between the first concentrated water chamber and the first fresh water chamber, and between the second concentrated water chamber and the second fresh water chamber, and anion exchange membranes are respectively used as intervals between the first fresh water chamber and the second concentrated water chamber, and between the second fresh water chamber and the third concentrated water chamber; if a plurality of cavity units are arranged, adjacent cavity units are arranged in sequence by taking the bipolar membrane as an interval or directly;
taking the example that the cystine mother liquor contains 17% of NaCl, since the cystine mother liquor contains 17 amino acids, and the isoelectric points of the amino acids are different, wherein the lowest isoelectric point is aspartic acid pI ═ 3, and the highest isoelectric point is arginine pI ═ 10.8, the cystine mother liquor is divided into two parts, one part is used as acidic mother liquor by adjusting the pH to 2.5-3 and is injected into an acidic mother liquor collecting box, and the other part is used as alkaline mother liquor by adjusting the pH to 10.5-11 and is injected into an alkaline mother liquor collecting box.
The direct current is passed through the bipolar membrane electrodialysis system 1, the circulating pumps of all the chambers are started, the acidic mother liquor is sucked into the acidic mother liquor circulating chamber I, the acidic mother liquor circulating chamber II and the acidic mother liquor circulating chamber III, the pH value of the acidic mother liquor is smaller than the isoelectric point of all the amino acids in the mother liquor, so that all the amino acids are positively charged and cannot migrate to the acid circulating chamber I or the acid circulating chamber II through the anion exchange membrane, and the Cl in the acidic mother liquor circulating chamber I, the acidic mother liquor circulating chamber II and the acidic mother liquor circulating chamber III
-Then passes through H generated on the anion exchange membrane and the bipolar membrane
+Combining in the first acid circulation chamber or the second acid circulation chamber to form HCl solution, and the positively charged amino acid in the second acid mother liquor circulation chamber is along with Na in the mother liquor
+Transfer to the first alkaline mother liquor circulation chamber through the cation exchange membrane, Na
+Then continuously transferring to the first alkali circulation chamber through the cation exchange membrane, Na
+With OH generated on the bipolar membrane
-Acting to produce NaOH solution;
the alkaline mother liquor is sucked into the first alkaline mother liquor circulating chamber, the second alkaline mother liquor circulating chamber andin the third alkaline mother liquor circulating chamber, because the pH value of the alkaline mother liquor is greater than the isoelectric point of all amino acids in the mother liquor, all the amino acids are negatively charged and cannot migrate to the first alkaline circulating chamber or the second alkaline circulating chamber through an anion exchange membrane, and Na in the first alkaline mother liquor circulating chamber, the second alkaline mother liquor circulating chamber and the third alkaline mother liquor circulating chamber
+Then permeate through OH generated on the cation exchange membrane and the bipolar membrane
-Combining in the first or second alkali circulation chamber to form NaOH solution, and mixing with Cl in the mother liquor
-Transferring into the third acidic mother liquor circulation chamber through an anion exchange membrane, wherein Cl is
-And then continuously transferring to the second acid circulation chamber through the anion exchange membrane, wherein the anions and H generated on the bipolar membrane
+Acting to produce HCl solution;
each chamber, the circulating pump connected with the chamber and the collecting box form a circulating loop respectively, wherein the acidic mother liquor circulating chamber I, the acidic mother liquor circulating chamber II and the acidic mother liquor circulating chamber III of all the chamber units can share one circulating pump and one acidic mother liquor collecting box; the first alkaline mother liquor circulating chamber, the second alkaline mother liquor circulating chamber and the third alkaline mother liquor circulating chamber of all the cavity units can share one circulating pump and one alkaline mother liquor collecting box; the acid circulation chambers I and II of all the cavity units can share one circulation pump and one acid liquid collection box; the first alkali circulation chamber and the second alkali circulation chamber of all the cavity unit can share one circulating pump and one alkali liquor collecting box;
when detecting Cl in the acid mother liquor collection box
-And Na in the alkaline solution collecting tank
+When the required target is reached, adding the two parts of mother liquor into a mixing chamber 2 for neutralization, adjusting the mixed mother liquor to be neutral, wherein the pH value of the compound amino acid is about 5-6, and a small amount of NaCl can be formed by the neutralization of an acid-base solution during mixing;
then, the mother liquor in the mixing chamber 2 after neutralization is added into a homogeneous membrane electrodialysis system 3 for desalination treatment, direct current is passed through the homogeneous membrane electrodialysis system 3, circulating pumps of all chambers are started, the mother liquor is sucked into a fresh water chamber, and Na in the mother liquor
+Through a cation exchange membrane, Cl
-Through an anion exchange membrane, Cl
-And Na
+NaCl is formed by combining in the concentrated water chamber, wherein a small amount of amino acid can enter the concentrated water chamber, but the solution in the concentrated water chamber can be completely returned to the original mother solution for recycling, so that the amino acid is not lost, and the problem of wastewater treatment is solved;
each chamber and the circulating pump and the collecting box connected with each chamber form a circulating loop respectively, wherein the concentrated water chambers of all the chamber units can share one circulating pump and one brine collecting box; the fresh water chambers of all the cavity units can share one circulating pump and one mother liquor collecting box;
and (3) after the desalting treatment of the homogeneous membrane electrodialysis system 3, obtaining a salt-free compound amino acid solution in a mother liquor collection box, and obtaining the salt-free compound amino acid product through conventional subsequent treatment (spray drying).
Example 2
On the basis of the embodiment 1, the mixing chamber 2 is further provided with an acidic mother liquor inlet and an alkaline mother liquor inlet, the acidic mother liquor inlet is connected with an acidic mother liquor collecting box in the bipolar membrane electrodialysis system 1 through a pipeline, the alkaline mother liquor inlet is also connected with an alkaline mother liquor collecting box in the bipolar membrane electrodialysis system 1 through a pipeline, the two pipelines are respectively provided with a control valve, the mixing chamber 2 is further provided with a mixed liquor outlet, the mixed liquor outlet is connected with a mother liquor collecting box in the homogeneous membrane electrodialysis system 3 through a pipeline, and the pipeline is provided with a control valve.
The acidic mother liquor and the alkaline mother liquor circulate in the bipolar membrane electrodialysis system 1, when the anion in the acidic mother liquor collecting box and the cation in the alkaline solution collecting box are detected to achieve the required targets, the acidic mother liquor and the alkaline mother liquor are controlled to enter the mixing chamber 2 through the control valve, the mixed mother liquor is adjusted to be neutral, the pH value of the compound amino acid is about 5-6, the mixed mother liquor enters the mother liquor collecting box of the homogeneous membrane electrodialysis system 3 through the control valve to be desalted, and namely the mixing chamber 2 plays a role in transition.
Example 3
The invention is based on the embodiment 1, and further relates to the bipolar membrane electrodialysis system1 and 3, 0.2 percent of Na is respectively added into the two electrode chambers
2SO
4Solution for electric conduction, in the homogeneous phase membrane electrodialysis system 3, add the aqueous solution in the concentrated water room respectively in concentrated water room one, concentrated water room two and concentrated water room three, and further, still include the flowmeter in the circulation circuit, be convenient for produce intermediate control, after the mother liquor gets into the device operation, still can utilize the chlorimeter to detect the chloride ion content in the stoste fast, guide production according to measured data.
Although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that various changes in the embodiments and/or modifications of the embodiments and/or portions thereof may be made, and all changes, equivalents, and modifications which fall within the spirit and scope of the invention are therefore intended to be embraced by the appended claims.
Claims (8)
1. The device for preparing the salt-free compound amino acid by using the cystine production waste liquid is characterized by comprising a bipolar membrane electrodialysis system (1), a mixing chamber (2) and a homogeneous membrane electrodialysis system (3), wherein the bipolar membrane electrodialysis system (1) and the homogeneous membrane electrodialysis system (3) respectively comprise electrode chambers on two sides and one or more chamber units clamped between the two electrode chambers, each of the bipolar membrane electrodialysis system (1) and the homogeneous membrane electrodialysis system (3) respectively forms a corresponding circulation loop with a circulating pump and a collecting box, and the mixing chamber (2) is used for adjusting the pH value of a mixed liquid of acidic mother liquid and alkaline mother liquid.
2. The apparatus for preparing salt-free compound amino acid by using cystine production waste liquid according to claim 1, characterized in that in the bipolar membrane electrodialysis system (1), each chamber unit is composed of an acid circulation chamber I, an acid mother liquid circulation chamber II, an alkaline mother liquid circulation chamber I, an alkaline circulation chamber I, an acid circulation chamber II, an acid mother liquid circulation chamber III, an alkaline mother liquid circulation chamber II, an alkaline mother liquid circulation chamber III and an alkaline circulation chamber II which are arranged in sequence; the electrode chamber adjacent to the first acid circulation chamber is an anode chamber, the anode chamber and the first acid circulation chamber are separated by a bipolar membrane, the electrode chamber adjacent to the second alkali circulation chamber is a cathode chamber, and the cathode chamber and the second alkali circulation chamber are separated by the bipolar membrane; anion exchange membranes are respectively used as intervals between the first acid circulation chamber and the first acid mother liquor circulation chamber, between the first acid mother liquor circulation chamber and the second acid mother liquor circulation chamber, between the second acid circulation chamber and the third acid mother liquor circulation chamber, and between the third acid mother liquor circulation chamber and the second alkaline mother liquor circulation chamber, and cation exchange membranes are respectively used as intervals between the second acid mother liquor circulation chamber and the first alkaline mother liquor circulation chamber, between the first alkaline mother liquor circulation chamber and the first alkaline circulation chamber, between the second alkaline mother liquor circulation chamber and the third alkaline mother liquor circulation chamber, and between the third alkaline mother liquor circulation chamber and the second alkaline circulation chamber; the pH range of the acidic mother liquor is 2.5-3, and the pH range of the alkaline mother liquor is 10.5-11; if a plurality of cavity units exist, adjacent cavity units are separated by the bipolar membrane.
3. The apparatus for preparing salt-free compound amino acid by using cystine production waste liquid according to claim 1, characterized in that, in the homogeneous membrane electrodialysis system (3), each chamber unit is composed of a concentrated water chamber I, a fresh water chamber I, a concentrated water chamber II, a fresh water chamber II and a concentrated water chamber III which are arranged in sequence; the electrode chamber adjacent to the first concentrated water chamber is an anode chamber, the anode chamber and the first concentrated water chamber are separated by a bipolar membrane, the electrode chamber adjacent to the third concentrated water chamber is a cathode chamber, and the cathode chamber and the third concentrated water chamber are separated by the bipolar membrane; cation exchange membranes are respectively used as intervals between the first concentrated water chamber and the first fresh water chamber, and between the second concentrated water chamber and the second fresh water chamber, and anion exchange membranes are respectively used as intervals between the first fresh water chamber and the second concentrated water chamber, and between the second fresh water chamber and the third concentrated water chamber; if a plurality of cavity units are provided, adjacent cavity units are arranged in sequence by taking the bipolar membrane as an interval or directly.
4. The device for preparing the salt-free compound amino acid by using the cystine production waste liquid as claimed in claim 1, wherein the mixing chamber (2) is provided with an acidic mother liquid inlet and an alkaline mother liquid inlet, the acidic mother liquid inlet is connected with an acidic mother liquid collecting box in the bipolar membrane electrodialysis system (1) through a pipeline, the alkaline mother liquid inlet is connected with an alkaline mother liquid collecting box in the bipolar membrane electrodialysis system (1) through a pipeline, and the pipelines are respectively provided with a control valve.
5. The device for preparing the salt-free compound amino acid by using the cystine production waste liquid as claimed in claim 4, wherein the mixing chamber (2) is further provided with a mixed liquid outlet, the mixed liquid outlet is connected with a mother liquid collecting box in the homogeneous membrane electrodialysis system (3) through a pipeline, and a control valve is arranged on the pipeline.
6. The apparatus for preparing salt-free compound amino acid from waste liquid from cystine production as claimed in claim 1, wherein 0.2% Na is added to each of the two electrode chambers in the bipolar membrane electrodialysis system (1) and the homogeneous membrane electrodialysis system (3)
2SO
4And (3) solution.
7. The apparatus for preparing salt-free compound amino acid by using cystine production waste liquid as claimed in claim 1, wherein said circulation loop further comprises a flow meter.
8. The apparatus for preparing a salt-free compound amino acid from a cystine production waste liquid according to claim 1, wherein in the homogeneous membrane electrodialysis system (3), aqueous solutions are respectively added into the first concentrated water chamber, the second concentrated water chamber and the third concentrated water chamber.
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| CN201910917649.2A CN110776387A (en) | 2019-09-26 | 2019-09-26 | Device for preparing salt-free compound amino acid by using cystine production waste liquid |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115246779A (en) * | 2021-09-13 | 2022-10-28 | 上海三及新材料科技有限公司 | L-carnitine extraction and purification process and device |
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| CN1865230A (en) * | 2006-06-14 | 2006-11-22 | 天津科技大学 | Method for extracting L-threonine from fermentation liquor |
| CN101967106A (en) * | 2010-09-01 | 2011-02-09 | 河北宏源化工有限公司 | Method for treating L-p-hydroxyphenylglycine desalting mother liquor by adopting bipolar membrane electrodialysis technology |
| CN102838240A (en) * | 2012-09-28 | 2012-12-26 | 武汉大学 | Method and system for recovering waste water generated in carbocisteine production |
| CN106582293A (en) * | 2016-12-13 | 2017-04-26 | 中国科学技术大学 | Carbon dioxide assisted bipolar membrane electrodialysis system and production method for amino acid production |
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| CN1865230A (en) * | 2006-06-14 | 2006-11-22 | 天津科技大学 | Method for extracting L-threonine from fermentation liquor |
| CN101967106A (en) * | 2010-09-01 | 2011-02-09 | 河北宏源化工有限公司 | Method for treating L-p-hydroxyphenylglycine desalting mother liquor by adopting bipolar membrane electrodialysis technology |
| CN102838240A (en) * | 2012-09-28 | 2012-12-26 | 武汉大学 | Method and system for recovering waste water generated in carbocisteine production |
| CN106582293A (en) * | 2016-12-13 | 2017-04-26 | 中国科学技术大学 | Carbon dioxide assisted bipolar membrane electrodialysis system and production method for amino acid production |
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| CN115246779A (en) * | 2021-09-13 | 2022-10-28 | 上海三及新材料科技有限公司 | L-carnitine extraction and purification process and device |
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